Process of treating mineral oils for increasing the yield of light-gravity oils.



DAVID '1. DAY, OF WASHINGTON, DISTRICT OE COLUMBIA.

PROCESS 01E TREATING MINERAL' OILS FOR INCREASING THE YIELD OF LIGHT-GRAVITY OILS.

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Application filed May 3, 1913, Serial No. 765,372.

To all whom it may concern:

Beit known that I, DAVID T. DAY, a citizen of the United States,residing at Washington, District of Columbia, have invented certain new and useful Improvements in Processes of Treating Mineral Oils for In creasing the Yield of Light-Gravity ()ils,

of which the following is a specification.

This invention relates to a process of increasing the production or yield of light gravity oils, such as gasolene, from petroleum or distillates, by facilitating and increasing the cracking or splitting up of the a heavier oils.

*The object of my invention is to provide taining little or no sulfur, such oils can be more easily decomposed by heat under the proper pressure, with the production of an increased percentage of distil'lates lighter in specific gravity than those which would be produced by the ordinary process of 51mple distillation.

I preferably conduct the distilhng operation in the presence of a substance containing hydrogen or hydrogen containing compounds-such as hydrogen carrying gas or vapor, and in the presence of a catalytic. agent or porous. contact substance, in acoordance with the process described in my Patents,'Nos. 826,089, July 17, 1906, and 1,004,632, October 3, 1911, I may add sulfur to the oil in the formof ammonium sulfid,

sodium sulfid, ironsulfid or copper sulfid or in the form of .sulfurete d hydrogen.

The sulfur compounds referred to are those compounds of sulfur with hydrogen and carbon and with hydrogen and other elements which' are comparatively easily broken up. This definitionapplies more for the sake of the applicability of these compounds to the process in this application,

ut does not apply .to compounds such as sulfates. In connection with this process sulfur ores are the ordinary sulfur ores of Specification of Letters Patent.

. Patented Apr. 3, IWLW. Renewed February 23, 1917. Serial No. 150,618.

commerce, particularly iron pyrites and cu piferous pyrites. Sulfids, but not sulfates, are to be regarded as available sulfur compounds within the meaning of the process in this application.

The matter constituting my invcntionwill be defined in the claims.

I will now describe my process more in detail in connection with the accompanying drawings, illustrating one form of apparatus in which the process may be performed and in which- Figure 1 represents a vertical longitudinal section of an oil still, with parts in elevation;

Fig. 2 represents a transverse section thereof on line 2-2, Fig. 1.

In the apparatus I provide a hydrogenator -D in the oil still A. This still is provided at its ends with removable heads a, a which are secured by bolts in slots as shown, or by swing bolts in a well known manner.

The hydrogenator D i made in the form of a manifold which can be removed or inserted in the cylinder A, as required. It is constructed with end heads B, B, each having a tube sheet connected by tubes d, and the heads having vapor chambers b, b. The front chamber 6 is open at the top for ad mitting oil vapor and the rear chamber 6 is closed except that it has a vapor outlet .pipe C, provided with a coupler c and a valve 0. Porous absorptive material econtact substance-is placed in the tubes d. Screw plugs b" are fitted in the outer plates of heads B.

A perforated supply pipe F, for admitting oil and gas is placed near the bottom of the still and is provided with a valve 7". An oil feed pipe F, having a valve f; also a hydrogen supply pipe G, having a valve 9 connect with pipe F. Apipe E, having a valve e may connect with pipe G, as shown, or at other suitable place, for admitting sulfureted' hydrogen gas to the oil in the still. Hydrogen or the well known water gas may be supplied hot from a generator H. The usual vapor outlet pipe J, having a valve 7', may connect with the still and with a condenser K. I preferably apply to the top of the still a pressure gage L and valve Z, a safety valve m, and a charging opening at,

having a tight fitting cover, for admitting a solid sulfur compound or other material.

The contact material 6 in the tubes d may no be iron by hydrogen, zinc dust, reduced pipe F, filling the same to the dotted line w and from one to fifteen per cent. of sulfur, or sulfur compound, or sulfur ore is added at the charging openingn. Instead of adding sulfur in solid form I may admit sul- -fureted hydrogen by pipe E and pass it from pipe F in fine streams up through the body of'oil at intervals during the distilling operation, The temperature is raised and the oil containing added sulfur is subjected to destructive distillation, Y or so called cracking by any of the well known processes. This splitting up of the heavier oils takes place at the ordinary pressure, but is accelerated by distilling under additional pressure; and in carrying out'my process'I raise .the pressure to a degree between 50 and 100 pounds per square inch above atmospheric pressure.

Ihave found that the cracking operation is greatly aided by passing a hydrogencarrying gas or vapor, such as hydrogen snlfid, ammonia, illuminating gas, or water,

gas, or steamthrough the oil and thence passing the connningled oil vapors and hydrogen from the space above the oil into the space I) and thence through the porous absorptive contact material e in the tubes d. A catalytic action'here takes place, resulting in the hydrogen being combined with the previously unsaturated hydro-car bons,resulting in the production of oils having a lower specific gravity and lower boiling point. I wish it understood that the cracking operation in the first instance is I much facilitated and increased by the added sulfur as above described, and thatas a result I produce an increased percentage of oils having a lower specific gravity and a lower boiling point. Sulfur is added at different stages of the process, as maybe necessary to maintain sulfur in the oil during distillation. a

The hydrogena-ting tubes d will be highly heated in the body of oil, and therefore, the oil vapors and hydrogen passing therethrough will be super-heated, which will facilitate the hydrogenating operation.

In order to regulate the temperature and maintain it at that degree most suitable for producing the cracking effect and for the hydrogenating operation, the valve 0' will be so set as to increase the pressure, and consequently the temperature of the body of oil'in the still. The pressure and temperature will thus be regulated for best effecting the cracking and the hydrogenating operations. a v

A stream of oil and hot hydrogen may be admitted simultaneously throng pipes 'F briqnets.

and G and discharged throu h pipes F up 1nto the oil. Sulfuretedhy rogen may be admitted at intervals as required through tween 250 C. and 350 O.,is not dependent upon the coincident hydrogenating o eration with a contact substance, as d scribed in my previous above mentioned patents, but the latter process supplements the cracking operation, and the two operations may be conducted together or successively with highly beneficial results, and the production of largely increased percentages of light specific gravity oils, as naphtha, benzin, etc.

The oils issuing from the condenser connecting with the vapor pipe C of any still are rich in sulfur compounds especially sulfureted hydrogen which is recovered to a large extent for subsequent use by passing hydrogen, or a gas containing the same, through the oil. The hydrogen is blown through the oil foragitating the same and a blown into the distillate oils serves to prevent oxidation of the oil by the sulfuric acid used in refining the same.

The sulfur remaining in the distillate is in such form as to be readily removable by the ordinary refining acid, or by agitation with fullers earth.

The oils obtained by this process are not only lower in boiling point than before, as the result of cracking, facilitated by the presence of added sulfur, but are-highly saturated compounds, and particularly easily refined.

The contact agent may be placed in the tube d by first removing the plugs b" and then inserting the substance in the form of By removing the plu at each end the substance may be pushe 'out with a rod. In practice there would preferably be a plug 6" in the plate opposite the end of each tube at each end 0 the manifold.

The vapor outlet pipe J with its valve 7', and connecting with a condenser K, may be used when the va ors are not being passed off through pi e The cracking operation with added sulfur could thus be carried out 50 and 100 pounds per square inch above drogenating operation.

process with sulfuric under high heat and ate. pressure between C., of distillate distilling between 150 and 300 (3., in the case of Mexican oil from well No. 4' of the Potre'ro' del Llano district, Mexico, Province of Vera Cruz, and determined that the distillates, even the 3% of naphtha distilling below 150, had particularly burnt and objectionable odor and would becharacterized by more than fifty per cent. of unsaturated hydrocarbons.

I immediately, with another portion of the same crude oil, repeated the distillation with the addition of five to ten per cent. of sulfur, the different proportions being used in different experiments. The result was an increase up to from seven to ten per cent. in the yield of naphtha and up to thirty to thirty-five per cent. of burning oil the distillatebetween 150 and 300 0., having a very marked improvement in the-odor, as soon as the sulfureted hydrogen accompanying these distillates was removed by the addition of a dilute solution of soda.

Further,by the treatment of the first dis-, tillate obtained, without the addition of sulfur, with sulfuric acid it was impossible to obtain what would be called a water white oil; whereas the treatment ofthe distillate obtained with the use of sulfur was quite easily refined. Further, both samples were tested as to the contents of unsaturated hydrocarbons, and while it was found that the distillate between 150 and 300 6., by the ordinary process contained over fifty per cent. of unsaturated hydrocarbons (according to themethodof treatment), by-shaking for fifteen minutes with an equal volume of sulfuric acid of 1.84 gravity. This test when applied to the oil from the sulfur distillation, showed less than twenty per cent.

of unsaturated hydrocarbons. These tests were repeated frequently and finally the tests were carried out ona' larger scale in iron stills in the laboratory of an oil refining company with similar results, and the proportionate improvement being greater with the better facilities when usin the iron retorts with the capacity of ten ga lons.

meme 1 a Having described my invention, what I claim, and desire to secure by Letters Patent, is

1. In the treatment of mineral oils to increase the yield of light gravity oils, the process, which consists in adding sulfur or a sulfur compound to a heavy oil, such as gas oil or other distillate having a higher boiling point than gasolene, and subjecting such oil under a cracking temperature and at a pressure greater than the atmospheric pressure, to distillation, and addingsulfur at intervals during the distillation, whereby the cracking of the heavier oils is facilitated and increased, resulting in the production of an increased percentage of gasolene.

2. In the treatment of mineral oils to increase the yield of light gravity oils, the process, which consists in adding sulfur or sulfur compounds to a comparatively heavy hydrocarbon oil, subjecting the same to distillation at a cracking temperature and at a regulated pressure greater than the atmospheric pressure, for facilitating the cracking operation, mixing" hydrogen carrying gas or vapor with the hot oil vapors of distillation in the still and passing the mixed vapors and gas through porous absorptive contact substances or a catalytic agent for improving the quality and increasing the percentage of light gravity oils.

3. In the treatment of mineral oil to increase the yield of light gravity oil, the

process, which consists in adding sulfur to the oil, subjecting the same to distillation for facilitating the cracking operation, passing streams of hydrogen carrying gas or vapor up through the body of oil being distilled, superheating the resulting mixture of hydrogen and oil vapors under pressure in contact with porous absorptive substances and thereby causing hydrogen to combine with the unsaturated oil.

4. In the treatment of mineral oils, the a process which consists of introducing sulfur I compounds, especially 'sulfureted hydrogen into oil distillates for the purpose of preventing oxidation of the distillate b the sulfuric acid used in refining said distillate,

and subsequently eliminating the sulfur by blowing and agitating with air or hydrogen. In testimony whereof I a my signature in presence of two witnesses.

DAD 'I. DAY. 

